Radiaxial fibrous calcites as low-magnesian calcite cement precipitated in a marine-meteoric mixing zone

Abstract Radiaxial fibrous calcite (RFC) has previously been interpreted as a marine or replacive cement. Study of the Dongjeom Formation (Early Ordovician), Korea, shows that RFC can form in marine‐meteoric mixing zones as a low‐magnesian calcite (LMC) cement. RFC in the shallow‐marine Dongjeom Formation occurs in arenaceous limestones at the top of a transgressive facies overlying a regressive facies. It shows well‐developed growth zonation, and lighter oxygen isotope values and more radiogenic strontium isotope ratios than those of Early Ordovician marine calcite. Such petrographic and chemical evidence indicates that the RFC was precipitated as a primary LMC cement in a marine and meteoric mixing zone. Owing to the unique environment of formation, the Dongjeom RFC is characterized by growth zonal fabric comprising alternating subzones, which may indicate precipitation from varying fluids. In addition, this study documents the importance of substrate for development of RFC. Early ‘nucleation’ for RFC occurred mainly on microcrystalline skeletal grains and internal sediments, whereas on homogeneously altered substrates, thin‐coated banding structure developed, ultimately forming coarse crystalline spar. This suggests that microcrystalline substrates are preferred sites for nucleation of RFC.     

Ferroan calcite replacement indicates former magnesian calcite skeletons

The replacement by ferroan calcite with preservation of the original structures can be used as a new criterion for identifying skeletons originally composed of high-magnesian calcite. This applies to bryozoa, rugose corals, echinoderms, many foraminifera, most ostracods, red algae, and serpulids. On the other hand, skeletons originally composed of low-magnesian calcite were never replaced by ferroan calcite, as shown by belemnites, brachiopods, and most of the pelecypods. Using this criterion, an original low-magnesian calcite composition is inferred for Tentaculites and some ostracods and foraminifera, whereas a previous high-magnesian calcite composition is inferred for trilobites, oligostegina and certain ooids. Chemical instability of high-magnesian calcite is suggested to be the driving force of the replacement by ferroan calcite. In most of the thirty-seven samples investigated, of Oligocene to Devonian age, the ferrous iron concentration of the interstitial fluid increased during diagenesis, as shown by well established sequences of cement A and B and fissure fill. This offers a relative time scale for diagenetic processes. Ferroan calcites contain up to 6 mol % FeCO₃ and up to 5 mol % MgCO₃. In this range of concentration, the distribution coefficients for Fe and Mg between calcite and solution at about 25°C are about 1 to 0-03, respectively, according to experiments. Possible sources of iron are iron oxides and hydroxides as well as clay minerals including glauconite. Though a submarine origin below the sediment surface is conceivable for ferroan calcite, there are serious limiting conditions such as low Eh and, at the same time, lack in sulphate-reducing bacteria. On the other hand, ferroan ‘dedolomite’, compositional zonality in individual ferroan calcite overgrowths, low δ¹⁸C and δ¹⁸O values, and low Mg concentrations point more to a meteoric-phreatic origin of many ferroan calcite occurrences.     

Site-specific incorporation of uranyl carbonate species at the calcite surface

Spatially resolved luminescence spectra from U(VI) co-precipitated at the (101?4) growth surface of synthetic calcite single crystals confirm heterogeneous incorporation corresponding to the distribution of structurally non-equivalent steps composing the vicinal surfaces of spiral growth hillocks. Spectral structure from U(VI) luminescence at the “-” vicinal regions and featureless, weak luminescence at the “+” vicinal regions are consistent with previously reported observations of enrichment at the former sites during calcite growth. Luminescence spectra differ between the non-equivalent regions of the crystal, with the spectral features from the “-” vicinal region corresponding to those observed in bulk calcite samples. Subtle spectral shifts are observed from U(VI) co-precipitated with microcrystalline calcite synthesized by a different method, and all of the U(VI)-calcite sample spectra differ significantly from that of U(VI) co-precipitated with aragonite.The step-selective incorporation of U(VI) can be explained by a proposed model in which the allowed orientation for adsorption of the dominant calcium uranyl triscarbonate species is controlled by the atomic arrangement at step edges. Differences in the tilt angles of carbonate groups between non-equivalent growth steps favor adsorption of the calcium uranyl triscarbonate species at “-” steps, as observed in experiments.     

Syntectonic hydrothermal calcite in a faulted carbonate platform margin (Albian of Jorrios, northern Spain)

ABSTRACT A calcite mass more than 1·5 km long and 20 m wide crops outs along the faulted margin of the Albian carbonate platform of Jorrios in northern Spain. The mass contains abundant dissolution cavities up to 7 m long and 1 m high, filled with cross‐stratified quartz sandstone and alternating sandstone–calcite laminae. Similar cavities are also present in a 50‐m‐wide zone of platform limestones adjacent to the calcite mass that are filled with limestone breccias and sandstone. The calcite mass has mean δ¹⁸O values of 19·6‰ (SMOW), whereas platform limestones have mean δ¹⁸O values of 24·4‰ (SMOW). Synsedimentary faulting of the carbonate margin and circulation of heated fault‐related waters resulted in replacement of a band of limestone by calcite. Soon after this replacement, dissolution by undersaturated fluids affected both the calcite mass and the adjacent limestones. Percolating marine quartz sand filled all dissolution cavities, sometimes alternating with precipitating calcite. The resulting cavities and fills, which recall products of meteoric diagenesis, are attributed to a hydrothermal origin based on their geometry, occurrence along the profile and synsedimentary tectonic relationships. The early faulting and diagenesis are related to local extensional tectonism in a large‐scale strike‐slip setting. Movements occurred during the early dispar/appenninica zone of the Late Albian.     

构造驱动大巴山前陆烃类流体排泄:含烃包裹体纤维状方解石脉证据

含烃包裹体纤维状方解石脉被认为是超高压下油气流体形成和排泄的标志。大巴山前陆构造带一些断裂和下古生界黑色泥岩和泥灰岩烃源岩微裂隙中分布有含烃包裹体纤维状方解石脉,成分分析表明其为低镁方解石。纤维状方解石脉δ13CVPDB和δ18OVPDB比围岩碳酸盐岩的明显变轻,前者δ13CVPDB和δ18OVPDB变化范围分别为-1.9%～-4.8‰和-8.4%～-12.8‰,后者分别为-1.7%～+3.1‰和-8.7%～-4.5‰,且δ13C与δ18O具有明显的线性关系,反映出纤维状方解石脉具有成岩有机流体与浅部流体混合的流体特征。纤维状方解石脉含有共生的固体沥青包裹体、含甲烷液相包裹体和气液二相盐水包裹体等多相态包裹体,其中沥青包裹体为油气运移的残余沥青。气液二相盐水包裹体均一温度主要位于140℃和196℃之间（峰值为179℃）,盐度较高（平均为9.7wt% NaCl）。分别应用盐水包裹体和甲烷包裹体等溶线P-T相图确定出含烃包裹体纤维状方解石脉形成的流体压力为150~200 MPa,属于异常超高压流体。地质和地球化学特征分析认为,大巴山含烃包裹体纤维状方解石脉不具有泥岩因压实成岩作用而形成的超高压流体特征。结合沉积和构造演化历史分析认为,印支碰撞造山运动和燕山前陆构造作用导致大巴山褶皱隆起并伴随天然气藏破坏和改造,挤压环境下的超高压构造应力驱动天然气流体排泄,大巴山前陆构造带含烃包裹体纤维状方解石脉就是超高压构造应力驱动天然气排泄的产物。     

Friction characteristics of Cd-rich carbonate films on calcite surfaces: implications for compositional differentiation at the nanometer scale

Lateral Force Microscopy (LFM) studies were carried out on cleaved calcite sections in contact with solutions supersaturated with respect to otavite (CdCO₃) or calcite-otavite solid solutions (SS) as a means to examine the potential for future application of LFM as a nanometer-scale mineral surface composition mapping technique. Layer-by-layer growth of surface films took place either by step advancement or by a surface nucleation and step advancement mechanisms. Friction vs. applied load data acquired on the films and the calcite substrate were successfully fitted to the Johnson Kendall Roberts (JKR) model for single asperity contacts. Following this model, friction differences between film and substrate at low loads were dictated by differences in adhesion, whereas at higher load they reflect differences in contact shear strength. In most experiments at fixed load, the film showed higher friction than the calcite surface, but the friction-load dependence for the different surfaces revealed that at low loads (0–40 nN), a calcian otavite film has lower friction than calcite; a result that is contrary to earlier LFM reports of the same system. Multilayer films of calcian-otavite displayed increasing friction with film thickness, consistent with the expectation that the film surface composition will become increasingly Cd-rich with increasing thickness. Both load- and thickness-dependence trends support the hypothesis that the contact shear strength correlates with the hydration enthalpy of the surface ions, thereby imparting friction sensitivity in the LFM to mineral-water interface composition.     

Fluid inclusions in skarns (carbonate replacement deposits)

Abstract Fluid inclusions in ore skarn minerals reflect the physiochemical nature of the solutions present during the skarn-forming process. Because of the dense nature of skarn minerals and the dynamic processes operative during skarn genesis, sufficient primary fluid inclusions are usually present. Ore skarn solutions, as opposed to metamorphic skarn or ore vein solutions, have much higher CaCl₂ contents and usually very high formation temperatures (>500°C) and salinities (>40 wt % T.D.S.). Temperatures and salinities generally decrease away from the solution source, both in time and space. The gradients found at greater distances from the source in distal (far from contact) skarns tend to be less (e.g. 210–350°C) for a particular skarn stage to that in proximal (near contact) skarns (e.g. 400–650°C). This information is useful for delineating the parts of such a hydrothermal system. Temperatures also tend to decrease with time, which is reflected by the superimposition of various overprinting, retrograde mineral stages. In a few areas (e.g. Naica, Mexico) intermittent boiling of ore solutions occurs, periodically elevating both temperatures and salinities, but commonly boiling only occurs early in skarn genesis just after an early, commonly lower temperature, phase. Most fluid inclusions represent a mix of‘exhaust’or reacted solutions with minor unreacted or new (pre-) ore solution components. Limited data on the distribution of elements present in fluid inclusions that do not normally take part in skarn genesis (Na, K and Cl) indicate that their proportions reflect the nature of the associated pluton. High KC1 contents are found in skarns adjacent to high K granitoids, whereas high NaCl contents are found in skarns adjacent to calcic granitoids. In many examples, daughter minerals present in minor proportions in opened fluid inclusion cavities reflect the metal characteristics of the ore solution. Small rare-earth metal, tungsten, zinc and copper daughter(?) minerals have been identified. The temperature and (or) salinity data for skarns of different metal or geological type is not particularly useful to delineate whether a skarn locality is part of a more complex, as yet unexplored system. Solutions in Pb–Zn skarns tend to be lower-temperature (150–400°C) and more dilute (<30 wt % T.D.S.) than in other skarn types, but exceptions occur.     

Composition of carbonate overgrowths produced on Iceland spar calcite crystals buried in bahamian carbonate-rich sediments

High-magnesium calcite overgrowths were precipitated on Iceland spar calcite crystals buried in Bahamian sediments. Their composition was within the range of carbonate cements in this area. The precipitation rate of the overgrowths was slower and the magnesium content higher than predicted from laboratory experiments, possibly due to adsorption of organic compounds.     

Pressure effect on magnesian calcite coating calcite and synthetic magnesian calcite seeds added to seawater in a closed system

When pure crystalline calcite seeds are added to supersaturated seawater, precipitation results in a coating which with time equilibrates at atmospheric pressure with seawater and corresponds to a calcite containing probably only 2 or 3% of MgCO₃ (mole fraction).If synthetic crystalline magnesian calcite is added, the surface layer equilibrates not only with respect to seawater but also in relation with the crystalline sites initiating precipitation. Adding Mg_0.03Ca_0.97CO₃ results in a coating with a solubility close to that of calcite. This confirms that the surface coating on pure calcite seeds contains about 2 or 3% MgCO₃ (K'_sp = 10?6.30).The surface layer precipitated on a synthetic Mg_0.08Ca_0.92CO₃ equilibrates finally with a carbonate more soluble than calcite (K'_sp = 10?5.94) corresponding to the seeds composition.Experiments at 1000 kg cm t-2 imply that when magnesian calcites are precipitated at the surface of calcite or magnesian calcite seeds, the precipitate must be hydrated, otherwise pressure accelerated recrystallization or rearrangement with loss of Mg would thermodynamically be impossible.By changing the pressure of a seawater sample originally saturated with a solid carbonate phase, changes in pH result from the effect of pressure on the dissociation constants of carbonic acid and boric acid causing either undersaturation or supersaturation with respect to the solid. By changing pressure we can show whether precipitation, dissolution and recrystallization are reversible processes if pH is taken as criteria of reversibility.     

Passive kimberlite intrusion into actively dilating dyke–fracture arrays: evidence from fibrous calcite veins and extensional fracture cleavage

Calcite veins are invariably associated with en-echelon kimberlite dyke–fracture arrays. A detailed microstructural study of veining indicates four vein types. Type I stretched or ataxial veins are defined by high aspect ratio calcite fibers that are crystallographically continuous with calcite of the kimberlite matrix wall rock, by elongated phenocrystic phlogopite with sharp crystal terminations centered on contacts between adjacent calcite fibers and by phenocrystic phlogopite that grows or extends across these veins. Type I vein mineralogy indicates syn-dilational crystallization of vein minerals in local tensional areas within the kimberlite. Vein Types II (stretched to syntaxial elongate-blocky) and III (antitaxial) indicate late crystallization vein mineral growth during subsequent or repeated dilation. Calcite fibers in Type I to Type III veins are orthogonal to the contacts of their host dykes regardless of the orientation of vein margins. Type IV calcite veins, with blocky or mosaic/polycrystalline textures, are attributed to minor post-intrusion extension, which was potentially accompanied by repeated kimberlite intrusion within a given dyke array. Syn-crystallization/syn-intrusion Type I veins and an ubiquitous dyke-parallel fracture cleavage, in a zone up to 4 m on either side of dyke contacts, suggest that en-echelon kimberlite dyke–fracture arrays occupied the approximate center of zones of active dilation within the brittle carapace of the upper crust. Type II and III veins indicate that extension or dilation continued, independently of an occupying kimberlite fluid phase, after initial intrusion. Arrested mobile hydrofracturing, under low differential stress within the upper brittle or seismic carapace of the continental crust, followed by repeated dilation of the dyke–fracture system, is proposed as a mechanism for producing the features observed in this study. The conditions constrained in this study indicate passive dyke intrusion into dilating fracture arrays during crustal extension.     

Formation of complex fibrous calcite veins in Upper Triassic strata of Wrangellia Terrain, British Columbia, Canada

Fibrous calcite veins are ubiquitous throughout the thinly bedded, organic-rich Upper Triassic marine mdrocks of the Queen Charlotte Islands and their lateral equivalents on Vancouver Island. These veins show variable and complex morphologies and can be grouped into several types: (a) simple; (b) anastomosing or composite; (c) boxwork; and (4) polygonal network oriented normal to bedding. Field, petrographic, and geochemical evidence suggest that vein opening, resulting from hydraulic fracturing due to elevated pore-fluid pressures, was an early phenomenon and occurred prior to significant compaction of the host sediments.Calcite fibers in the veins are up to 30 mm long and commonly oriented perpendicular to the wall but locally display conical structures. Fibrous calcites, with the exception of those in boxwork veins, are generally non-ferroan and dull to very weakly orange luminescent. The boxwork calcites are ferroan, zoned and show dull luminescence with some bright rims.δ¹⁸O values range from −8.2 to −21.6‰ (PDB) and δ¹³C values range from 2.0 to −4.4‰ (PDB). Although some variations are present among the different morphological types of calcite veins, oxygen and carbon isotopic values display important variations when compared geographically. The most depleted oxygen and carbon isotopic values are those of boxwork calcite and they are associated with areas where the effects of early Mesozoic plutonism were most severe. Precipitation of boxwork fibrous calcites is interpreted to have been related to hydrothermal discharge into unconsolidated host sediment, rather than to later burial. Although the hydrothermal influence on the formation of vein calcite is related to geological events specific to the Wrangellia Terrain, this study provides an alternative mechanism for the generation of fibrous calcite veins and demonstrates the local importance of hydrothermal input in the evolution of pore-water chemistry.     

The genesis of calcite in carbonate rocks of the sedimentary basins: Evidence from the stable carbon and oxygen isotopes composition

The distributions of stable carbon and oxygen isotopes in modern and ancient limestones of various types were studied. Carbonate samples from modern sediments were collected in the Black and Barents Seas. Ancient carbonates were represented by Upper Jurassic (Kimmeridgian-Tithonian) limestones from the central part of the West Siberian basin. Carbonate samples include remains of modern and Upper Jurassic fauna, carbonate crust from sediments of the Black Sea, carbonate tube from sediments of the Barents Sea, and Upper Jurassic limestone from the carbonate layer found at top of Abalak, bottom of Bazhenov deposits in the central part of the West Siberian basin. According to the results of the isotope analysis and comparison with modern carbonates, Upper Jurassic limestones of the West Siberian basin belong to the group of methane-derived carbonates and precipitated as a result of anaerobic oxidation of methane (AOM). Fractures in limestones are filled with secondary calcite.     

Biogenic and abiogenic low-Mg calcite (bLMC and aLMC): Evaluation of seawater-REE composition,water masses and carbonate diagenesis

The ΣREE and shale-normalized (PAAS) REE_SN values of modern brachiopods (biogenic low-Mg calcite: bLMC) represented by several species from high- to low latitudes, from shallow- to deep waters and from warm- and cold-water environments, define three distinct average ‘seawater’ trends. The warm- and cold-water brachiopods define two indistinguishable (p < 0.050) groups that mimic open-ocean seawater REE chemistry, exhibiting the typical LREE enrichment with a slightly positive to negative Ce anomaly followed by an otherwise invariant series. Other recent brachiopods from an essentially siliciclastic seabed environment are distinct in both ΣREE and REE_SN trends from the previous two populations, showing a slight enrichment in the MREEs and an increasing trend in the HREEs. Other groups of modern brachiopods are characterized by elevated REE_SN trends relative to the ‘normal’ groups as well as by complexity of the series trends. The most characteristic feature is the decrease in the HREEs in these brachiopods from areas of unusual productivity (i.e., such as upwelling currents, fluvial input and aerosol dust deposition). Preserved brachiopods from the Eocene and Silurian exhibit REE_SN trends and Ce anomalies similar to that of the ‘open-ocean’ modern brachiopods, although, their enriched ΣREE concentrations suggest precipitation of bLMC influenced by extrinsic environmental conditions.Preservation of the bLMC was tested by comparing the ΣREE and REE_SN trends of preserved Eocene brachiopods to those of Oligocene brachiopods that were altered in an open diagenetic system in the presence of phreatic meteoric-water. The altered bLMC is enriched by approximately one order of magnitude in both ΣREE and REE_SN trends relative to that in bLMC of their preserved counterparts. Similarly, the ΣREE and REE_SN of preserved Silurian brachiopod bLMC were compared to those of their enclosing altered lime mudstone, which exhibits features of partly closed system, phreatic meteoric-water diagenesis. Despite these differences in the diagenetic alteration systems and processes, the ΣREEs and REE_SN trends of the bLMC of altered brachiopods and of originally mixed mineralogy lime mudstones (now diagenetic low-Mg calcite) are enriched by about one order of magnitude relative to those observed in the coeval and preserved bLMC.In contrast to the changes in ΣREE and REE_SN of carbonates exposed to phreatic meteoric-water diagenesis, are the REE compositions of late burial calcite cements precipitated in diagenetically open systems from burial fluids. The ΣREE and REE_SN trends of the burial cements mimic those of their host lime mudstone, with all showing slight LREE enrichment and slight HREE depletion, exhibiting a ‘chevron’ pattern of the REE_SN trends. The overall enrichment or depletion of the cement REE_SN trends relative to that of their respective host rock material reflects not only the openness of the diagenetic system, but also strong differences in the elemental and REE compositions of the burial fluids. Evaluation of the (Ce/Ce*)_SN and La = (Pr/Pr*)_SN anomalies suggests precipitation of the burial calcite cements essentially in equilibrium with their source fluids.     

Elasticity of calcite: thermal evolution

The elastic properties of calcite have been determined by Brillouin spectroscopy for temperatures up to 600 °C. The results reveal that the variations of the aggregate bulk (K _VRH) and shear (G _VRH) moduli of calcite with respect to temperature can be approximately expressed as follows: $$\begin{aligned} K_{{{\text{VRH}}}} ({\text{GPa}}) & = 79.57-0.0230\;T\, (T\;{\text{in}}\;^{^\circ } {\text{C}}) \\G_{{{\text{VRH}}}} ({\text{GPa}}) & = 32.23 - 0.0097\;T. \\\end{aligned}$$ This indicates a nearly constant Poisson’s ratio (0.322) for calcite from 22 to 600 °C. A further analysis shows that the compressibility along the c axis (β _||) and that perpendicular to the c axis have comparable contributions to the volume compressibility of calcite, although the contribution of β _|| decreases with an increase in the temperature.     

Aqueous cadmium uptake by calcite: a stirred flow-through reactor study

Uptake of cadmium ions from solution by a natural Mg-containing calcite was investigated in stirred flow-through reactor experiments. Input NaCl solutions were pre-equilibrated with calcite (pH 8.0) or not (pH 6.0), prior to being spiked with CdCl₂. For water residence times in the reactor less than 0.5 h, irreversible uptake of Cd by diffusion into the bulk crystal had a minor effect on the measured cadmium breakthrough curves, hence allowing us to quantify “fast” Cd²⁺ adsorption. At equal aqueous activities of Cd²⁺, adsorption was systematically lower for the pre-equilibrated input solutions. The effect of variable solution composition on Cd²⁺ adsorption was reproduced by a Ca²⁺-Cd²⁺ cation exchange model and by a surface complexation model for the calcite-aqueous solution interface. For the range of experimental conditions tested, the latter model predicted binding of aqueous Ca²⁺ and Cd²⁺ to the same population of carbonate surface sites. Under these circumstances, both adsorption models were equivalent. Desorption released 80 to 100% of sorbed cadmium, confirming that fast uptake of Cd²⁺ was mainly due to binding at surface sites. Slow, irreversible cadmium uptake by the solid phase was measured in flow-through reactor experiments with water residence times exceeding 0.7 h. The process exhibited first-order kinetics with respect to the concentration of adsorbed Cd²⁺, with a linear rate constant at 25°C of 0.03 h⁻¹. Assuming that diffusion into the calcite lattice was the mechanism of slow uptake, a Cd²⁺ solid-state diffusion coefficient of 8.5×10⁻²¹ cm² s⁻¹ was calculated. Adsorbed Cd²⁺ had a pronounced effect on the dissolution kinetics of calcite. At maximum Cd²⁺ surface coverage (∼10⁻⁵ mol m⁻²), the calcite dissolution rate was 75% slower than measured under initially cadmium-free conditions. Upon desorption of cadmium, the dissolution rate increased again but remained below its initial value. Thus, the calcite surface structure and reactivity retained a memory of the adsorbed Cd²⁺ cations after their removal.     

Magnesian calcite stabilities: A reevaluation

Equilibrium constants at stoichiometric saturation with respect to various magnesian calcite compositions were measured using free-drift dissolution rate data and inverse time plots to estimate equilibrium pH. The equilibrium constants determined for two ultrasonically cleaned and annealed biogenic magnesian calcites (12 and 18 mole % MgCO₃) in CaCl₂ + MgCl₂ media at two Mg:Ca molar ratios (1:5 and 5:1) are about three times smaller than those previously reported by Plummer and Mackenzie (1974). These equilibrium constants are not affected by changes in initial pH value, solid:solution ratio, or solution Mg:Ca molar ratio when the ion activity product is expressed in the fractional exponent form. Other models for expression of the equilibrium ion activity product fail to yield consistent values in solutions of different Mg:Ca molar ratios.Experiments performed using crushed samples not ultrasonically cleaned and annealed yield equilibrium constants which vary with solid:solution ratio. Those performed at high solid:solution ratios yield values which approach those previously reported. Submicron size particles and crystal strain induced by crushing the biogenic carbonates may cause more rapid dissolution rates and, hence, overestimation of the solubility of samples not prepared so as to minimize these effects. Thus, the large range in reported solubilities of magnesium calcites may be a result of differences in sample preparation procedure.The results of these measurements shift the thermodynamic equivalence point of aragonite and magnesian calcite from 7.5 mole % MgCO₃ up to 12 mole % MgCO₃ and prompt a reassessment of models for carbonate diagenetic reactions in natural environments.     

Differences in grain growth of calcite: a field-based modeling approach

Normal grain growth of calcite was investigated by combining grain size analysis of calcite across the contact aureole of the Adamello pluton, and grain growth modeling based on a thermal model of the surroundings of the pluton. In an unbiased model system, i.e., location dependent variations in temperature-time path, 2/3 and 1/3 of grain growth occurs during pro- and retrograde metamorphism at all locations, respectively. In contrast to this idealized situation, in the field example three groups can be distinguished, which are characterized by variations in their grain size versus temperature relationships: Group I occurs at low temperatures and the grain size remains constant because nano-scale second phase particles of organic origin inhibit grain growth in the calcite aggregates under these conditions. In the presence of an aqueous fluid, these second phases decay at a temperature of about 350 °C enabling the onset of grain growth in calcite. In the following growth period, fluid-enhanced group II and slower group III growth occurs. For group II a continuous and intense grain size increase with T is typical while the grain growth decreases with T for group III. None of the observed trends correlate with experimentally based grain growth kinetics, probably due to differences between nature and experiment which have not yet been investigated (e.g., porosity, second phases). Therefore, grain growth modeling was used to iteratively improve the correlation between measured and modeled grain sizes by optimizing activation energy (Q), pre-exponential factor (k₀) and grain size exponent (n). For n=2, Q of 350 kJ/mol, k₀ of 1.7×10²¹ mⁿs^–1 and Q of 35 kJ/mol, k₀ of 2.5×10^-5 mⁿs^–1 were obtained for group II and III, respectively. With respect to future work, field-data based grain growth modeling might be a promising tool for investigating the influences of secondary effects like porosity and second phases on grain growth in nature, and to unravel differences between nature and experiment.Editorial responsibility: J. Hoefs